Water-displacing agent



United States Patent WATER-DISPLACING AGENT No Drawing. ApplicationFebruary 24, 1956 Serial No. 567,471

16 Claims. (Cl. 106-14) This invention relates to water displacingagents which will preferentially adsorb on a metallic surface displacingany residual moisture. Particularly, the invention relates to waterdisplacing agents which may be added to rust preventive compositions toenhance their rust preventive properties.

It is usual to protect metal parts from corrosion by applying atemporary rust preventive between manufacturing steps and prior tostorage or packaging. The parts to be protected are often coated with anundesirable film of water. The water film may come from cooling orcutting fluids, rinsing baths, or from condensation of water vapor fromthe atmosphere. This water film must be removed in order for the rustpreventive to be effective. A common method of removing this film is topass the metal parts. through a heated drying oven prior to theapplication of the rust preventive. This process is both slow andexpensive. A more efiicient and desirable method is to embody into therust preventive compound a material which will preferentially adsorbonto the metallic surface thereby displacing any residual moisture andpermitting a continuous rust preventive coating. The condensationproducts of alkylene oxides and fatty acidpolyamine compounds have beenfound to be excellent additives for this purpose and are the subject ofthis invention.

The alkylene oxide condensates of the fatty acidpolyamines of thisinvention are formed by reacting an alkylene oxide with a fattyacid-polyarnine compound which in turn has been formed by reacting afatty acid and a polyamine.

It has been found that these materials, when blended in fluid type rustpreventives in proportions ranging from about 0.1% to 10.0% by Weight,materially increase the effectiveness of the rust preventive againstrusting caused by the presence of residual moisture. It is preferred touse about 1.0% to 5.0% by weight of the additives of this invention.

The additive materials of this invention may be used with removable typefluid rust preventive compositions. Such rust preventive compositionscontain a solvent or oil base material, a rust preventive agent, andfrequently contain waxes which aid in forming a protective film.Additional additives may also be contained in the rust preventivecomposition such as anti-oxidants, metal deactivators, dyes, and otherusual type additives.

The oleaginous base material or solvent may be volatile or non-volatile.Generally, a mineral oil product is used, such as Stoddard Solvent;naphthas, preferably naphthas having initial boiling points of about 180F. to 310 F., and final boiling points of about 210 F. to 500 F.; gasoil; lubricating oil, preferably having a viscosity of about 35 to 1000S. S. U. at 210 F.; and petrolatum. Vegetable or animal oils may beused, as well as synthetic oils, e. g., esters such as dibasic acidesters. Mixtures of any of the above solvent materials may also be used.

Rust preventive agents which may be used include the C to C fatty acidpartial esters of aliphatic polyhydric alcohols having about 3 to 12,preferably 3 to 8, carbon atoms. monooleate, glyceryl monooleate,pentaerythritol monooleate, the di-oleates of sorbitan, mannitan,pentaerythritol and related polyhydric alcohols, the correspondingpartial stearic and palmitic acid esters of these alcohols, and partialesters of these alcohols made from mixtures of these fatty acids.

Another class of rust preventive compounds are the oil soluble sulfonatesoaps, preferably of alkali or alkaline earth metals, such as calcium orsodium salts of mahogany sulfonic acids, said sulfonic acids havingmolecular weights of about 350 to 520 and preferably about 430 to 520.

Other rust preventives which may be used are oxidized wax esters, metalxanthates, metal phenolates, metal phenol sulfides, metal naphthenates,metal organo phosphates and thiophosphates, vegetable and animal fattyoils, etc. Wool grease (degras) is a particularly suitable additive whena residual coating which will adhere Well to metal is desired.

Various mixtures of the above rust inhibitors may also be used. Forexample, metal sulfonate salts of the types mentioned are particularlydesirable in combination with the partial esters of pentaerythritol inrust preventive coating compositions.

Various waxes may be used in the rust preventive com position for thepurpose of forming a heavier film on the surface to be protected. Thewaxes may be crystalline or microcrystalline and may be derived fromanimal, vegetable or mineral origns or may be synthetic waxes. However,the most important of these waxes are the parafiin waxes derived frompetroleum. These paraflin Waxes may be either normal or iso-paraffin andpreferably have melting points of about 100 to 200 F.

In general, the compositions of the invention are rust preventivecompositions comprising a major amount of an oleaginous base, a minoramount, usually about .5 to 30%, preferably about 3% to 15% by weight,of a rust preventive agent, and about .1 to 10%, preferably 1 to 5% byWeight of a Water displacing agent. Waxes in amounts of about 1 to 40%,preferably 1 to 15% by weight, based on the total composition, may alsobe added Where a heavier residual coating is desired.

Compositions of the invention embodying the use of partial esters as therust inhibiting agent, will contain by weight, about 0.5 to 15 parts,preferably about 3 to 10 parts esters; about 0.1 to 10 parts, preferablyabout 1 to 5 parts, of the water displacing agent of the invention; andabout to 99 parts, preferably about to 96 parts of an organic solvent oroleaginous base material. The oleaginous base material may be a straightlubricating oil, preferably a mineral lubricating oil, or a volatilehydrocarbon solvent, such as naphtha. Mixtures, in any proportions, oflubricating oil and naphtha may also be used. Waxes, preferably paraffinWaxes, may be added in amounts of about 1 to 40, preferably 1 to 15weight and most preferably in amounts of about 2 to 8% by weight, basedon the total composition.

Compositions of the invention embodying the use of oil soluble petroleumsulfonates as the rust inhibiting agent will consist by weight, of about.5 to 15, preferably 2 to 8 parts of the oil-soluble alkali or alkalineearth. metal sulfonate; about .1 to 10, preferably about 1 to 5 parts ofa water displacing agent of the invention; and about 75 to 99 parts,preferably about 87 to 97 parts of a solvent. The solvent may be alubricating oil or a volatile solvent such as naphtha, or mixturesthereof. To this composition may be added about 2 to 25, preferablyExamples of these partial esters are: sorbitan about 2 to 10 weightpercent, based on the total composition, of degras. Wax may also beadded in amounts of about 1 to 40 weight percent preferably about 1 to15 weight percent, and most preferably about 2 to 8 weight percent,based on the total composition.

The rust inhibiting composition may also contain several different rustpreventive agents. For example, an oil soluble metal sulfonate and apartial ester might both be used in the same composition.

The fatty acid-polyamine compound is prepared by reacting aboutequi-molar portions of the polyamine and fatty acid by well knownmethods. Although not known with certainty, the main reaction isbelieved to be a condensation reaction as follows;

wherein, R is an aliphatic hydrocarbon radical which may be saturated orunsaturated, constituting the non-carboxylic portion of a fatty acid ofabout 10 to 22 carbon atoms and which may also contain substituents,such as hydroxy, halogen, or others, for hydrogen on one or more of thecarbon atoms; n is an integer of about 1 to 4 and preferably about 2 to3; and x is a whole number of about to 3 and preferably is 0 to 1. Theabove equation is believed to define the main reaction and the reactionproducts, however, other reactions may take place. Temperatures'maintained within the range of 110 C. to 250 C. for about 1.5 to 6 hoursare suitable for this reaction and temperatures maintained within therange of 120 C. to 160 C. for about 2 to 4 hours are preferred. Thewater formed during the reaction can be removed from the reactionmixture by evaporation or distillation. In the case where the water isremoved by distillation a water entraining agent such as xylene,toluene, benzene, naphtha and others, may be used.

Operable polyamines include those containing primary amine groups suchas ethylene diamine, propylene diamine, butylene diamine, etc., and alsoinclude polyamines Which may contain both primary and secondary aminegroups such as diethylene triamine, triethylene tetramine, tetraethylenepentamine, dipropylene triamine, tripropylene pentamine, and the like.

Operable fatty acids are those having about 10 to 22 carbon atoms,preferably about 12 to 18 carbon atoms and which may be saturated orunsaturated, and which may be substituted for hydrogen on one or more ofthe carbon atoms. Examples of such acids include stearic, hydroxystearic, such as l2-hydroxy stearic, di-hydroxy stearic, poly-hydroxystearic, capric, lauric, myristic, palmitic, oleic, linoleic, linolinic,ricinoleic, erucic, behenic and others.

When the fatty acid-polyamine compound has been formed, it is furtherreacted with from about 1 to 10 moles, preferably 2 to moles, of analkylene oxide by methods well known in the art. The primary reaction isbelieved to be as follows:

\ CH-CHr-O -H wherein, R is an aliphatic hydrocarbon radical, which maybe saturated or unsaturated, constituting the non-carboxylic portion ofa fatty acid of about to 22 carbon atoms and which also may containsubstituents for hy drogen on one or more of the carbon atoms; n is aninteger of about 1 to 4, preferably 2 to 3; x is a whole number of 0 to3, preferably 0 to 1; R is a radical selected 4 from the groupconsisting of hydrogen and alkyl radicals containing about 1 to 3 carbonatoms, a is an integer of about 1 to 10, preferably about 2 to 5; b andc are integers of about 0 to 10 each, preferably 0 to 5, providedhowever, that the sum of b-I-c must equal a.

The above equation is believed to represent the main reaction that takesplace. However, other reactions may take place in which alkylene oxidegroups may attach onto the intermediate nitrogen atoms (i. e., thenitrogen atoms in the group -C-NC).

The reaction should be carried out at a temperature within the rangefrom about 25 C. to 200 C., preferably C. to 150 C. and at pressuresfrom about 1 to 10 atmospheres, preferably 2 to 6 atmospheres for about1 to 24 hours, preferably 2 to 5 hours. A trace of water or an aqueoussolution of alkali or alkaline earth hydroxides may be used as acatalyst. The reaction product may be used without further purification.

Operable alkylene oxides include ethylene oxide, propylene oxide,butylene oxide and the like.

The invention will be more clearly explained by reference to thefollowing examples.

EXAMPLE I One mole (282 grams) of oleic acid and 1 mole (60 grams) ofethylene diamine and 680 grams of xylene (a water entraining agent) wereadded to a flask equipped with a stirrer, thermometer and a refluxcondenser hav-, ing a water trap. The mixture was stirred at roomtemperature for about one-half hour to form the ammonium salt. Thereaction mixture was then heated to about 140150 C. and refluxed at thistemperature for about two and a half hours during which time one mole(18 cc.) of water was collected in the water trap. The remaining mixturewas then distilled under a vacuum of 10 mm. mercury over a period ofabout one hour to re: move the xylene. The resulting fattyacid-polyamine product, which was a dark, viscous liquid, was believedto be chiefly an amide-amine having the formula:

This product was then placed in a stainless steel pres sure bomb and atrace (about 0.5 cc.) of a 2 normal sodium hydroxide solution was added.This was then heated to C. under a pressure of 4 atmospheres. Threemoles of ethylene oxide were slowly bubbled into the bomb over a time ofabout 40 minutes while the temperature of the contents was maintained at100120 C. by external cooling. After the 3 moles of ethylene oxide wereadded, the temperature of the bomb was held at about 110 C. for 3 morehours to complete the reaction.

The product was a dark, viscous liquid which was used without furtherpurification.

EXAMPLE II This was similar to Example I except diethylene triamine wasused in place of the ethylene diamine. The reaction product was acondensate of 3 moles of ethylene oxide with the reaction productprepared by reacting equi-molar amounts of oleic acid and diethylenetriamine. The effectiveness of these materials as water displacingagents was determined in the following manner.

Water displacing test procedure Two inch by three inch sandblastedpanels of mild steel are dipped in water to deposit a water film overthe panel. The wetted panel is then submerged in the test blend for 15seconds without agitation. The panel is then stored in a humiditycabinet in an upright position for 1 hour at a temperature of 77 F. andat a relative humidity of 100%. At the end of this time, the panel isrinsed in heptane and examined for rust and discoloration.

The following examples illustrate the rust preventive effectiveness ofcompositions utilizing the water displacing agents of the presentinvention.

EXAMPLE HI The water displacing agents of Examples I and H were added toa base which was a rust preventive composition. Said baseconsisted of3.75% by weight of a mineral oil with a viscosity of about 100 S. S. U.at 100 F. and 3.75 weight percent of sodium soap of a petroleum sulfonicacid having an average molecular weight of 450; 7.5 weight percent ofneutral degras; and 85 weight percent of a hydrocarbon solvent naphthahaving a flash point of 105 F. and a mid-boiling point of 338 F. and afinal boiling point of about 397 F. The following data was A is thereaction product of Example I, which is a condensate of 3 moles ofethylene oxide and 1 mole of a fatty acid-polyamine compound prepared byreacting 1 mole of oleic acid and 1 mole of ethylene diamine.

1 is the reaction product of Example II which is a condensate of 3 molesof ethylene oxide and 1 mole of a fatty acid-polyamine compoundprlepared by reacting 1 mole of oleic acid and 1 mole of diethylene ramine.

EXAMPLE IV Various other compositions were prepared which embodied waterdisplacing agents of the invention. Water displacing tests were also runon these compositions, and the results are listed in Table 11 below:

TABLE IV.--HUMIDITY CABINET LIFE.

JAN-H-79Z Humidity Cabinet Lite, hrs., Av-

Composition, Weight Percent erage of 2 runs As seen from the abovetable, the addition to the rust preventive composition of 1% of thewater displacing agents prepared in Examples I and II improved theresistance to rusting.

What is claimed is:

1. A rust inhibiting composition comprising a major proportion of anoleaginous solvent, a rust preventive proportion of a rust preventive,and a water displacing proportion of a water displacing agent, saidwater displacing agent being the condensation product of (1) the fattyacid-polyamine reaction product of substantially equi-molar portions ofa fatty acid containing about 10 to 22 carbon atoms and a polyaminehaving the formula:

wherein, n is an integer of about 1 to 4 and x is an integer of about 0to 3, and (2) about 1 to 10 moles of an alkylene oxide having theformula:

wherein R is a member selected from the group consisting TABLE II.WATERDISPLAOIN G AGENT Composition, Weight Percent E'ri'g h elting Point)Refined Paraffin Wax 6.0. Clear. No. Stain.

l Hydrolcagbio n mineral lubricating oil having an A. P. I. gravity of40.3 degrees, flash point of 270 F., and a viscosity of 51.9

S.S.U at 00 7 l l iydrocarbon solvent naphtha having a flash point of105 F., a mid-boiling point of 338 F. and a final boiling point oi aboutEarium soap of a sulfonic acid having a molecular weight of about 440.It is a concentrate of soap by weightin a mineral oil having a viscosityof about 100 S. S. U. at 100 F.

As can be seen from the above tables, the additives of this inventionwere very efiective in preventing rust caused by residual moisture on ametallic surface.

EXAMPLE V A further test was run to determine the effect of thecompounds of the invention on the life of a rust preventive. Several ofthe compositions of Example III were subjected to the humidity test. Thehumidity tests were run in the humidity cabinet described in theMilitary Specification JAN-H-792, which is recognized standard humiditytest. The test panels were sandblasted, rinsed in boiling naphtha andboiling methanol, and cooled to room temperature in a desiccator. Thepanels were dipped for 2 minutes in the rust preventive composition,withdrawn and hung for 25 hours at room temperature prior to beingplaced in the cabinet.

of hydrogen and alkyl radicals containing from about 1 to 3 carbonatoms.

2. A rust inhibiting composition according to claim 1 wherein said waterdisplacing agent is present in amounts of about 0.1 to 10% by weight ofthe total composition.

3. A rust inhibiting composition according to claim 1 wherein said waterdisplacing agent is present in amounts of about 1.0 to 5.0% by weight ofthe total composition.

4. A rust inhibiting composition according to claim 1 in which saidwater displacing agent is the condensation product of (a) 3 moles ofethylene oxide and (b) 1 mole of the fatty acid-polyamine reactionproduct of equal moles of oleic acid and ethylene diamine.

5. A rust inhibiting composition according to claim 1 in which saidwater displacing agent is the reaction product of 3 moles of ethyleneoxide and 1 mole of the condensation product prepared by reacting 1 moleof oleic acid and 1 mole of diethylene triamine.

6. A rust inhibiting composition according to claim 1 which containsabout 1 to 40 weight percent of a wax.

7. A liquid rust preventive composition comprising about 75 to 99 partsof an oleaginous base, about 0.5 to 15 parts of a partial ester of afatty acid having about 12 to 22 carbon atoms per molecule and analiphatic polyhydric alcohol having about 3 to 12 carbon atoms permolecule, and about .1 to 10% of a water displacing agent, said waterdisplacing agent being the condensation product of (1) the fattyacid-polyamine reaction product of substantially equi-molar portions ofa fatty acid containing about 10 to 22 carbon atoms and a polyaminehaving the formula:

2( n 2n' ).-r n 2n 2 wherein n is an integer of about 1 to 4 and x is aninteger of about to 3, and (2) about 1 to moles of an alkylene oxidehaving the formula:

R-OH-CH wherein R is a member selected from the group consisting ofhydrogen and alkyl radicals containing about 1 to 3 carbon atoms.

8. A liquid rust preventive composition comprising about 75 to 99 partsof an ole-aginous base, about 0.5 to parts of an oil soluble metal soapof a sulfonic acid, and about 0.1 to 10 parts of a water displacingagent, said Water displacing agent being the condensation product of (1)the fatty acid-polyarnine reaction product of substantially equi-molarportions of a fatty acid containing about 10 to 22 carbon atoms and apolyamine having the formula:

wherein, n is an integer of about 1 to 4 and x is an integer of about 0to 3, and (2) about 1 to 10 moles of an alkylene oxide having theformula:

wherein, R is a member selected from the group consisting of hydrogenand alkyl radicals containing from about 1 to 3 carbon atoms.

9. A composition according to claim 8 which contains about 2 to 25weight percent degras, based on the total composition.

10. A composition according to claim 8 which contains about 1 to 40weight percent Wax, based on the total composition.

11. A rust preventive composition which comprises (1) about 96 to 99weight percent of a base material consisting of 3.75 weight percent of asodium soap of a petroleum sulfonic acid having an average molecularweight of 450, 3.75 weight percent of a mineral oil having a viscosityof about 100 S. S. U. at 100 F., 7.5 weight percent of neutral degras;85 weight percent of a naphtha; and (2) about 1 to 4 weight percent ofthe condensation product of 3 moles of ethylene oxide and 1 mole of thereaction product of equal moles of oleic acid and ethylene diamine.

12. A rust preventive composition which comprises (1) 96 to 99 weightpercent of a base material consisting of 3.75 weight percent of a sodiumsoap of a petroleum sulfonic acid having an average molecular weight of450, 3.75 weight percent of a mineral oil having a viscosity of about100 S. S. U. at 100 F., 7.5 weight percent of neutral degras; weightpercent naphtha; and (2) about 1 to 4 weight percent of the reactionproduct of 3 moles of ethylene oxide and 1 mole of the condensationprodnot of equal moles of oleic acid and diethylene triamine.

13. A rust preventive composition comprising by weight, 5.0% sorbitanmonooleate, 5.0% paraffin wax, 10.0% hydrocarbon mineral lubricatingoil, 77.0% hydrocarbon solvent naphtha, and 3% of the condensationproduct of 3 moles of ethylene oxide and 1 mole of the reaction productof equal moles of oleic acid and ethylene diamine.

14. A rust preventive composition comprising by weight, 5.0% sorbitanmonooleate, 5.0% parafiin Wax; 10.0% hydrocarbon lubricating oil, 77.0%hydrocarbon solvent naphtha, and 3% of the condensation product of 3moles of ethylene oxide and 1 mole of the reaction product prepared byreacting 1 mole of oleic acid and 1 mole of diethylene triamine.

15. A rust preventive composition comprising by weight 4.0% of a refinedparafiin wax, 13.3% of a hydrocarbon mineral lubricating oil, 77.0% ofnaphtha, 2.7% of a barium soap of a sulfonic acid having a molecularweight of about 440, and 3.0% of the condensation product of 3 moles ofethylene oxide and 1 mole of the reaction product of equal moles ofoleic acid and ethylene diamine.

16. An improved process for the temporary protection of metal parts fromcorrosion from residual moisture which comprises coating said metalparts with a rust preventive composition which contains a waterdisplacing amount of a water displacing agent, said water displacingagent being the condensation product of (1) the fatty acid-polyaminereaction product of substantially equimolar portions of a fatty acidcontaining about 10 to 22 carbon atoms and a polyamine having theformula:

2( n 2n )a: n 2n 2 wherein, n is an integer of about 1 to 4 and x is aninteger of about 0 to 3, and (2) about 1 to 10 moles of an alkyleneoxide having the formula:

wherein R is a member selected from the group consisting of hydrogen andalkyl radicals containing from about 1 to 3 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS2,002,613 Orthner et al. May 28, 1935 2,085,706 Schoeller et al. June29, 1937 2,453,816 Schindler et a1 Nov. 16, 1948 2,509,786 SchiermeierMay 30, 1950 2,681,354 Kelley et al. June 15, 1954

7. A LIQUID RUST PREVENTIVE COMPOSITION COMPRISNG ABOUT 75 TO 99 PARTSOF AN OLEAGINOUS BASE, ABOUT 0.5 TO 15 PARTS OF A PARTIAL ESTER OF AFATTY ACID HAVING ABOUT 12 TO 22 CARBON ATOMS PER MOLECULE AND ANALIPHATIC POLYHYDRIC ALCOHOL HAVING ABOUT 3 TO 12 CARBON ATOMS PERMOLECULE, AND ABOUT .1 TO 10% OF WATER DISPLACING AGENT, SAID WATERDISPLACING AGENT BEING THE CONDENSATION PRODUCT (1) THE FATTYACID-POLYAMINE REACTION PRODUCT OF SUBSTANTIALLY EQUI-MOLAR PORTIONS OFA FATTY ACID CONTAINING ABOUT 10 TO 22 CARBON ATOMS AND A POLYAMINEHAVING THE FORMULA